CN106450354B - A kind of hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst - Google Patents
A kind of hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst Download PDFInfo
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- CN106450354B CN106450354B CN201610873701.5A CN201610873701A CN106450354B CN 106450354 B CN106450354 B CN 106450354B CN 201610873701 A CN201610873701 A CN 201610873701A CN 106450354 B CN106450354 B CN 106450354B
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
It is to be put into baking oven after being sufficiently mixed GO and urea to carry out nitrating heat treatment the invention discloses a kind of hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst；The GO of nitrating is crushed and is added after deionized water carries out ultrasonic disperse 0.5h and is transferred to hydrothermal reaction kettle, cobalt salt is added in magnetic agitation 20min, continues to stir 10min, sealing reaction kettle carries out hydro-thermal reaction；After hydro-thermal reaction, hydrazine hydrate is added and adjusts pH value of solution to 10 with concentrated ammonia liquor, sealing reaction kettle continues hydrothermal reduction reaction, obtains nitrogen-doped graphene and loads cobalt composite material.Using nitrogen-doped graphene prepared by the present invention load cobalt composite material as oxygen reduction electro-catalyst, the cyclic voltammetric reduction spike potential in 0.1M KOH solution is -0.18V (vs.Ag/AgCl), take-off potential -0.1V (vs.Ag/AgCl).
Description
One, technical field
The present invention relates to a kind of synthetic method of oxygen reduction reaction elctro-catalyst, specifically a kind of nitrogen-doped graphene
The hydrothermal synthesis method of Supported Co oxygen reduction reaction elctro-catalyst.
Two, background technique
In oxygen reduction reaction elctro-catalyst, most preferably Pt and Pt Base Metal loads carbon to current the most frequently used and catalytic activity
Composite material, but due to Pt scarcity of resources, expensive, use process the defects of there are catalyst granules aggregations, therefore for many years
Carry out researchers in the cost for reducing oxygen reduction reaction elctro-catalyst, finds novel preparation method and novel carrier material etc.
Aspect has carried out a large amount of research work, is broadly divided into Pt base and non-Pt base catalyst.
Base metals (the Niu G such as Fe, Co, Ni, Cu are mainly adulterated in the work of Pt base catalyst on the basis of Pt/C
et al,Nano Letters,2016,16(6),3850-3857；Salgadoa J et al, Applied Catalysis B:
Environmental, 2005,57 (4), 283-290；Mani et al,Journal of Power Source,2011,196
(2), 666-673), since this kind of base metal can only replace Pt on a small quantity, it can not fundamentally reduce production cost.
Non- Pt base catalyst can be divided into transistion metal compound base and transition metal based catalysts.Transistion metal compound
Mainly there are transient metal sulfide, transition metal oxide (including spinel-type and Ca-Ti ore type) and transient metal complex
Deng (Feng Y J et al, Fuel Cells, 2000,10 (1), 77-83；Wu Z S et al,Journal of the
American Chemical Society,2012,134,9082-9085；Liang Y et al,Nature Materials,
2011,10,780-786), such transistion metal compound as elctro-catalyst electric conductivity and in terms of also deposit
In certain defect.The research of transition metal based catalysts relatively concentrates on the chemical combination of the transition metal such as Co, Fe or Cu Yu the atom containing N
Object coordination is obtained transition metal and is mixed jointly with N by high-temperature roasting under inert gas protection after directly or with carbon carrier mixing
Miscellaneous oxygen reduction electro-catalyst (Qiao X et al, ACS Sustainable Chemistry&Engineering, 2016,4,
4131-4136；Zhou J et al,Physical Chemistry Chemical Physics,2014,16,15787-
15791), also have by transition metal precursor under ammonia atmosphere, high-temperature roasting obtains transition metal/N/C compound oxygen reduction electricity
Catalyst (Herranz Juan et al, the Journal of Physical Chemistry, 2007,111 (51),
19033-19042)。
Three, summary of the invention
The present invention is intended to provide a kind of hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst,
Heating is blended using urea and GO first and carries out N doping vario-property, the GO area load cobalt for then adulterating under hydrothermal conditions N
Compound, then nitrogen-doped graphene load cobalt composite material is obtained with hydrazine hydrate reduction under hydrothermal conditions.It is prepared by the present invention
Nitrogen-doped graphene loads cobalt composite material as oxygen reduction electro-catalyst, in 0.1molL-1Cyclic voltammetric in KOH solution
Reduction spike potential is -0.18V (vs.Ag/AgCl), take-off potential -0.1V (vs.Ag/AgCl).
The hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst of the present invention, including walk as follows
It is rapid:
It is put into baking oven after graphene oxide (GO) and urea are sufficiently mixed and carries out nitrating heat treatment；After nitrating is heat-treated
GO be crushed to 100 mesh or more and be added in deionized water, be added cobalt salt after ultrasonic disperse 0.5h, move into hydrothermal reaction kettle,
It is dispersed with stirring uniformly, seals reaction kettle, the hydro-thermal reaction 4~for 24 hours at 140~200 DEG C；After hydro-thermal reaction, hydration is added
Hydrazine simultaneously adjusts solution ph to 10 with ammonium hydroxide, seals reaction kettle, and thermal reduction reaction 4~for 24 hours is lauched in 110~180 DEG C；After cooling
Solution is filtered using decompression, is washed twice with deionized water and dehydrated alcohol respectively, and nitrogen-doped graphene load is obtained after dry
Cobalt composite material.
The graphene oxide that the present invention uses is graphite powder using partial size less than 20 μm as raw material, using conventional Hummer
Graphene oxide (GO) (Wang H et al, the Angewandte Chemie, 2011,123,7502- that method is prepared
7506)。
The mass ratio of the GO and urea is 1:3~1:10.
The temperature control of nitrating heat treatment at 120~180 DEG C, the time control of nitrating heat treatment 4~for 24 hours.
The cobalt salt be selected from cobalt nitrate, cobalt chloride or cobalt acetate, 0~2 times of the additive amount GO mass of cobalt salt, preferably 0.5
~2 times.
The dosage of the hydrazine hydrate is 10~40 times of GO mass.
The temperature of the drying is 60~250 DEG C, preferably 160~250 DEG C；Drying time be 2~for 24 hours, preferably 2~10h.
Cobalt composite material, which is loaded, as elctro-catalyst using nitrogen-doped graphene prepared by the present invention carries out electrocatalytic oxidation reduction
Reaction, process are as follows:
Electrocatalytic oxidation reduction reaction is carried out in a three-electrode cell, and wherein working electrode is load 0.4mg
cm-2The glass-carbon electrode of nitrogen-doped graphene Supported Co elctro-catalyst, is platinum electrode to electrode, and reference electrode is saturation silver chlorate
Electrode, electrolyte 0.1molL-1KOH solution.With 50mLmin before test-1Flow be passed through oxygen or nitrogen
30min makes gas in solution reach saturation.
The preparation of working electrode is to take 5mg elctro-catalyst powder, and dehydrated alcohol and 5wt%Nafion is added, and (volume ratio is
Uniform pulpous state liquid is obtained after mixed solution 350 μ L, ultrasonic disperse 0.5h 6:1), and 5.5 μ L pulpous state drops is taken to be added to 0.196cm2
Glassy carbon electrode surface, the electrochemical property tests such as cyclic voltammetric and polarization curve are carried out after dry 12h under room temperature, wherein recycling
Voltammetric scan rate is 50mVs-1, linear sweep rate 5mVs-1。
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, the present invention carries out N doping reaction with GO under lower heat treatment temperature using cheap urea, remains GO
Surface active group abundant.
2, the present invention carries out metal precursor load and reduction reaction, system to N doping graphene oxide using hydro-thermal reaction
Preparation Method is simple and easy to control, and reaction condition is mild, and assay reproducibility is good.
3, nitrogen-doped graphene Supported Co elctro-catalyst prepared by the present invention is within the scope of the cyclic voltammetry scan of -1~0V
Do not occur other reduction peaks, shows the highly selective of oxygen reduction reaction.
Four, Detailed description of the invention
Fig. 1 is the SEM photograph that nitrogen-doped graphene prepared by embodiment 1 loads cobalt composite material；
Fig. 2 is the SEM photograph that nitrogen-doped graphene prepared by embodiment 2 loads cobalt composite material；
Fig. 3 is that the nitrogen-doped graphene of Examples 1 to 3 preparation loads cobalt composite material XRD spectrum；
Fig. 4 is that the nitrogen-doped graphene of Examples 1 to 3 preparation loads working electrode prepared by cobalt composite material and Pt/C
Cyclic voltammetry curve；
Fig. 5 is that the nitrogen-doped graphene of Examples 1 to 3 preparation loads working electrode prepared by cobalt composite material and Pt/C
The resulting polarization curve under 1600 revs/min of revolving speed.
Fig. 6 is that nitrogen-doped graphene prepared by example 1 loads working electrode prepared by cobalt composite material in 0.1mol
L-1Oxygen reduction reaction Koutecky-Levich matched curve figure in KOH solution.As seen from the figure, prepared hydrogen reduction electricity is urged
Oxygen reduction reaction electron transfer number of the agent at 0.4V, 0.5V, 0.6V and 0.7V is 4, shows the height of oxygen reduction reaction
Selectivity.
Five, specific embodiment
Embodiments of the present invention are described in detail below in conjunction with portion of techniques scheme:
Embodiment 1:
1, the graphite powder using partial size less than 20 μm prepares graphene oxide using conventional Hummer method as raw material
(GO)；
2, GO and urea are mixed according to the ratio of mass ratio 1:10 and is put into 160 DEG C of baking ovens progress nitrating heat treatments after milling
The GO of nitrating is crushed and is washed with deionized after cooling by 6h, and ultrasonic disperse 0.5h in deionized water is then added and obtains concentration
For 1.5gL-1Uniform dispersion；The cobalt nitrate crystals of 0.5 times of GO mass are added into the dispersion liquid, are dispersed with stirring uniformly
Mixed liquor is transferred to hydrothermal reaction kettle afterwards, the hydro-thermal reaction 12h at 160 DEG C；Reaction kettle is opened after cooling, and 15 times of GO mass are added
Hydrazine hydrate, adjusting solution ph with ammonium hydroxide is 10, seals reaction kettle, and 180 DEG C are lauched thermal reduction reaction 10h, and reaction solution is cooling
It is filtered, is washed twice with deionized water and dehydrated alcohol respectively, 160 DEG C of dry 10h obtain nitrogen-doped graphene using decompression afterwards
Load cobalt composite material.
3, the composite material of the above-mentioned preparation of 5mg is taken, addition dehydrated alcohol is mixed with 5wt%Nafion (volume ratio 6:1's)
350 μ L of solution is closed, uniform pulpous state liquid is obtained after ultrasonic disperse 0.5h, 5.5 μ L pulpous state drops is taken to be added to 0.196cm2Glass carbon electricity
Pole surface, it is 0.4mgcm that load capacity, which is prepared, after dry 12h under room temperature-2Working electrode, select platinum electrode for electricity
Pole, saturation silver chloride electrode are reference electrode, 0.1molL-1Potassium hydroxide solution be electrolyte, with 50mLmin-1's
Flow leads to oxygen 30min, and gas in solution is made to reach saturation.Using electrochemical workstation, the regular worker in three-electrode cell
Make electrode and with 50mVs-1It sweeps speed and obtains cyclic voltammetry curve；Working electrode revolving speed is 400~2500rpmmin-1, linearly
Sweep speed is 5mVs-1The lower polarization curve for obtaining different rotating speeds.
The oxygen reduction reaction elctro-catalyst that the present embodiment obtains is in 0.1molL-1Cyclic voltammetric reduction peak in KOH solution
Current potential is -0.18V (vs.Ag/AgCl), take-off potential -0.11V (vs.Ag/AgCl).
Embodiment 2:
1, the graphite powder using partial size less than 20 μm prepares graphene oxide using conventional Hummer method as raw material
(GO)；
2, GO and urea are mixed according to the ratio of mass ratio 1:3 and is put into 180 DEG C of baking ovens progress nitrating heat treatments after milling
The GO of nitrating is crushed and is washed with deionized after cooling by 4h, and ultrasonic disperse 0.5h in deionized water is then added and obtains concentration
For 1.5gL-1Uniform dispersion；The dispersion liquid is transferred to hydrothermal reaction kettle, the hydro-thermal reaction 4h at 140 DEG C；After cooling
Reaction kettle is opened, adjusting solution ph with ammonium hydroxide is 10, is added after the hydrazine hydrate of 10 times of GO mass and seals reaction kettle, at 110 DEG C
Hydrothermal reduction reacts 4h, is filtered after reaction solution is cooling using decompression, is washed twice, 60 DEG C with deionized water and dehydrated alcohol respectively
Drying for 24 hours, obtains nitrogen-doped graphene load cobalt composite material.
3, electrode performance test is the same as embodiment 1.
The oxygen reduction reaction elctro-catalyst that the present embodiment obtains is in 0.1molL-1Cyclic voltammetric reduction peak in KOH solution
Current potential is -0.21V (vs.Ag/AgCl), take-off potential -0.14V (vs.Ag/AgCl).
The present embodiment is only used for explaining: not plus cobalt also just has apparent hydrogen reduction electrocatalysis characteristic, and only catalytic effect does not have
Have the good of Supported Co, but the mode of this nitrating be it is novel, so this example can also be used for the catalyst of Supported Co into
Row comparison.
Embodiment 3:
1, the graphite powder using partial size less than 20 μm prepares graphene oxide using conventional Hummer method as raw material
(GO)；
2, GO and urea are mixed according to the ratio of mass ratio 1:5 and is put into 120 DEG C of baking ovens progress nitrating heat treatments after milling
For 24 hours, the GO of nitrating is crushed and is washed with deionized after cooling, ultrasonic disperse 0.5h in deionized water is then added and obtains concentration
For 1.5gL-1Uniform dispersion；The cobalt acetate crystal of twice of GO mass is added into the dispersion liquid, is dispersed with stirring uniformly
Mixed liquor is transferred to hydrothermal reaction kettle afterwards, the hydro-thermal reaction 4h at 200 DEG C；Reaction kettle is opened after cooling, and 40 times of GO mass are added
Hydrazine hydrate, adjusting solution ph with ammonium hydroxide is 10, seals reaction kettle, and 140 DEG C are lauched thermal reduction reaction for 24 hours, and reaction solution is cooling
It is filtered, is washed twice with deionized water and dehydrated alcohol respectively, 250 DEG C of dry 2h obtain nitrogen-doped graphene using decompression afterwards
Load cobalt composite material.
3, electrode performance test is the same as embodiment 1.
The oxygen reduction reaction elctro-catalyst that the present embodiment obtains is in 0.1molL-1Cyclic voltammetric reduction peak in KOH solution
Current potential is -0.18V (vs.Ag/AgCl), take-off potential -0.1V (vs.Ag/AgCl).
Claims (5)
1. a kind of hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst, it is characterised in that including such as
Lower step:
It is put into baking oven after graphene oxide and urea are sufficiently mixed and carries out nitrating heat treatment；Oxidation stone after nitrating is heat-treated
Black alkene is crushed to 100 mesh or more and is added in deionized water, and cobalt salt is added after ultrasonic disperse 0.5h, moves into hydrothermal reaction kettle,
It is dispersed with stirring uniformly, seals reaction kettle, the hydro-thermal reaction 4~for 24 hours at 140~200 DEG C；After hydro-thermal reaction, hydration is added
Hydrazine simultaneously adjusts solution ph to 10 with ammonium hydroxide, seals reaction kettle, and thermal reduction reaction 4~for 24 hours is lauched in 110~180 DEG C；After cooling
Solution is filtered using decompression, is washed respectively with deionized water and dehydrated alcohol, and it is multiple that nitrogen-doped graphene Supported Co is obtained after dry
Condensation material；
The temperature control of nitrating heat treatment at 120~180 DEG C, the time control of nitrating heat treatment 4~for 24 hours；
The cobalt salt is selected from cobalt nitrate, cobalt chloride or cobalt acetate, and the additive amount of cobalt salt is 0.5~2 times of graphene oxide quality.
2. synthetic method according to claim 1, it is characterised in that:
The mass ratio of graphene oxide and urea is 1:3~1:10.
3. synthetic method according to claim 1, it is characterised in that:
The dosage of hydrazine hydrate is 10~40 times of graphene oxide quality.
4. synthetic method according to claim 1, it is characterised in that:
The temperature of the drying be 60~250 DEG C, drying time be 2~for 24 hours.
5. synthetic method according to claim 4, it is characterised in that:
The temperature of the drying is 160~250 DEG C, and drying time is 2~10h.
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| CN110479340B (en) * | 2018-05-14 | 2022-05-27 | 南京理工大学 | Nano cobalt/nitrogen doped graphene composite material and preparation method thereof |
| CN109675603A (en) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | A kind of carbon-supported catalysts and its preparation method and application of silica protection |
| CN111987327B (en) * | 2020-08-26 | 2022-07-08 | 福州大学 | Pt/Co nanoparticle-loaded nitrogen-doped graphene and preparation method thereof |
| CN112156801A (en) * | 2020-09-27 | 2021-01-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of nitrogen-doped axial carbon fiber/graphene-loaded cobalt nano electro-catalyst |
| CN112695342A (en) * | 2020-12-28 | 2021-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cobalt/nitrogen-doped graphene and carbon nanofiber composite material, product and application thereof |
| CN114628697B (en) * | 2022-03-11 | 2024-03-08 | 山东大学 | FeCo alloy@nitrogen doped graphene hierarchical pore aerogel serving as oxygen reduction reaction catalyst and preparation method and application thereof |
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